Electrochimica Acta 52 (2007) 5512–5516

Ligand effects in heterogeneous catalysis and electrochemistry

T. Bligaard ∗ , J.K. Nørskov
Center for Atomic-scale Materials Design, Department of Physics, Building 307, NanoDTU,
Technical University of Denmark, DK-2800 Lyngby, Denmark
Received 29 November 2006; received in revised form 4 February 2007; accepted 4 February 2007
Available online 20 February 2007

Abstract
Ligand effects in surface reactivity are discussed on the basis of extensive density functional theory calculations. The d-band model is reviewed
and it is shown that it can be used to rationalize trends in reactivity in heterogeneous catalysis and electrochemistry.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Trends; Alloys; Ligand effects; d-Band model; Electronic structure

1. Introduction cal reactions, where the complexity of the electrolyte–surface

Modern density functional theory (DFT) calculations provide
a method to resolve the electronic structure of even rather com-
plicated model systems with adequate accuracy at a reasonable
computational cost [1]. A class of systems for which DFT has
been applied with considerable success involve chemical reac-
tions taking place on solid surfaces [2]. Both in heterogeneous
catalysis and in electrochemistry it is important to understand
the chemical bonding of atoms and molecules to transition metal
surfaces. The best transition metal catalyst for a given reaction
will to a large extent be determined by the ability of the metal to
bond the key reaction intermediates in just the right way [3,4].
When going through the periodic table, the adsorption proper-
ties of the pure metals vary enormously, and it is the changes
in the electronic structure of the metallic surface which lead
to these variations. An atomic-scale understanding of phenom-
ena in both heterogeneous catalysis and in electrochemistry is
therefore intimately tied to an understanding of the electronic
structure of the catalyst or electrode surfaces.
Only a small fraction of the research being carried out in the
fields of electrochemistry and heterogeneous catalysis is related
to electronic structure theory, and this seems to suggest that in
both classes of systems large complexities are present which are
necessary to take into account in order to actually understand
specific reactions. This is perhaps most true for electrochemi-
∗ Corresponding author. Tel.: +45 45253179; fax: +45 45932399.
E-mail address: bligaard@fysik.dtu.dk (T. Bligaard).
interface with varying ion concentrations and local field effects
seems larger than for a gas phase heterogeneous reaction. Some
surface catalyzed reactions are understood in elaborate detail
both from experiment and from theory. One example is ammo-
nia synthesis [5], which is one of the most studied reactions from
the electronic structure point of view [6]. Calculating the reac-
tion rate for a particular catalyst is an enormous task [5], but it
turns out that if the goal is to determine which of the elements in
the periodic table is the best catalyst, a much simpler approach
is sufficient [7]. The reason for this is that the change in elec-
tronic structure from one element to the next in the periodic table
implies large variations in adsorption and activation energies for
the elementary steps of this reaction. In spite of changes in the
specific adsorption sites for the intermediates, changes in rela-
tive coverages of various intermediates the experimental trends
are systematically reproduced by adding only the simplest level
of micro-kinetic analysis to the results of the electronic structure
calculations [7].
Recently simple models [8–19] have been introduced to treat
electrochemical systems using DFT calculations, and it has
become possible to start performing the same type of trend stud-
ies for electrochemical reactions as those that have been known
in heterogeneous catalysis. Two cases where trends studies have
been initiated are the oxygen reduction reaction [18] and the
hydrogen evolution reaction [19]. Whereas the ideas behind such
trend studies have been known and used in the field of electro-
chemistry for half a century [20], the advent of DFT calculations
have allowed for the development of systematic databases of
adsorption energies. One benefit of this development is that DFT

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.02.041
 T. Bligaard, J.K. Nørskov / Electrochimica Acta 52 (2007) 5512–5516
calculations can be used as the basis for the search after new elec-
trode materials [21]. Another benefit is that the entire established
apparatus of electronic structure theory now can be applied to
the surfaces of electrodes under electrochemical reaction condi-
tions.
In order to understand the variation in adsorption energies
that form the basis for describing trends in surface reactivity in
both heterogeneous catalysis and electrochemistry it is important
to develop simple models or concepts being able to rationalize
the data. A particularly useful model in heterogeneous catalysis,
which is often used to relate changes in the electronic structure
of transition metal surfaces to changes in chemical reactivity is
the d-band model [22], and in the following we will review some
of the features of this model.
2. The d-band model
In the d-band model variations in adsorption energies and
activation barriers for a given reaction from one transition metal
to the next are given, to a first approximation, by variations in the
coupling between the adsorbates levels and the transition metal
d-bands. The adsorbate–surface bond is viewed as consisting of
two contributions:
E = E0 + Ed
where E0 is the bond energy contribution from the coupling of
the adsorbate states to the free-electron-like s-electrons and Ed
is the contribution from the extra interaction with the transition
metal d-electrons. The two-step model is illustrated in Fig. 1.
One of the basic assumptions of the d-band model is that
E0 is independent of the metal. This is a quite reasonable first
approximation since the s-bands of transition metals are broad
and it is always half filled. It is not a rigorous approximation,
though. It will for instance fail when metal particles get small
enough that the sp levels do not form a continuous (on the scale
of the metal–adsorbate coupling strength) spectrum. It will also
fail for metals where the d-states do not contribute to the bond-
ing at all. The other basic assumption is that we can estimate
the d-contribution as the non-self-consistent one-electron energy
change as [23]:
 layer is strained so that the coupling, Vdd , of the metal d-states to
Ed ∼ = ε(n (ε) − n(ε)) dε
Fig. 1. Schematic illustration of the formation of a chemical bond between an
adsorbate valence level and the s- and d-states of a transition metal surface. From
Ref. [22].
5513
Fig. 2. Schematic illustration of the coupling between bandwidth and d-band
center for a band with a fixed number of d-electrons. When the bandwidth is
decreasing the only way of maintaining the number of d-electrons is to shift up
the center of the band.
Here n (ε) and n(ε) are the adsorbate-induced densities of
states with and without the d-coupling included, respectively.
In general the coupling of the adsorbate states to the metal
d-bands will depend on a number of parameters, the energy of
the adsorbate state(s), εa , the d-density of states projected onto
the metal atoms in direct contact to the adsorbate, nd (ε), and the
coupling matrix element between the adsorbate and the surface
states. In the following we will focus on situations where a given
adsorbate couples to a specific kind of transition metal atom
complex (a CO molecule bonding to a Pt atom, for instance)
and study the effect of varying the surroundings (or ligands) to
the relevant metal atoms (changing the nearest neighbor atoms
of the Pt to which CO bonds, for instance). In these cases εa and
the matrix elements are constant and only the nd (ε) will vary.
We will focus on the first moment of the nd (ε), the center of the
d-band, εd , as the simplest descriptor, and show that it describes
variations in the adsorption energies quite well.
It should be noted that apart from the d-band center, the inter-
action energy will depend on the shape and width of the projected
d-density of states, nd (ε). These variations are, however often
coupled to the d-band center variations, and can therefore be
lumped into that dependence. To illustrate this point, consider
a situation where the width (the second moment, W, of nd (ε)
is decreased for some reason—it could be because the surface
the neighboring metal d-states is smaller (W ∼ |Vdd |) or because
the number of metal neighbors (the coordination number, NM ) is
decreased by creating a step or a kink on the surface (W ∼ NM 0.5 ).
Changing W for a fixed εd − εF would change the number of d-
electrons. It is generally found that the number of d-electrons
does not change for a given kind of metal, and the system com-
pensates for this by shifting the d-states up in energy as illustrated
in Fig. 2.
We will here consider two classes of trends determined
largely by variations in εd − εF . Variations due to changes in
surface structure and variations due to alloying.
3. Variations due to changes in surface structure
The d-band center can be varied for a specific transition metal
by varying the structure. As mentioned above, the bandwidth
5514 T. Bligaard, J.K. Nørskov / Electrochimica Acta 52 (2007) 5512–5516

Fig. 3. Calculated d-projected densities of states for different Pt surfaces with

decreasing atom density. The hexagonally reconstructed (1 0 0) surface, the
close-packed (1 1 1) surface, the step atoms on a (2 1 1) surface and the kink
atoms on a (1 1 8 5) surface. From Ref. [24].

depends on the coordination number of the metal and this leads

to substantial variations in the d-band centers [24]. The atoms in
the most close-packed (1 1 1) surface of Pt have a coordination
number of 9. In the more open (1 0 0) surface it is 8 and at a step
or at the (1 1 0) surface it is 7. At a kink the coordination number
is as low as 6. As shown in Fig. 3, this leads to variations in the
d-band center of almost 1 eV, and the chemisorption energy of
CO varies by a similar amount (see Fig. 4). The fact that steps
bind CO stronger than the flat surfaces is in excellent agreement
with experimental evidence [25,26].
The Pt surfaces have a tendency to restructure into overlayers
with an even higher density of Pt atoms than the close packed
(1 1 1) surface [27]. Since the Pt atoms are closer to each other
here than in the (1 1 1) surface, the overlap matrix elements and
hence the bandwidth will be larger, the d-bands are lower and
consequently these reconstructed surface bind CO even weaker
than the (1 1 1) surface.
The reconstructed Pt surfaces are examples of strained over- Fig. 4. Correlation between adsorption energies of various adsorbates and d-
layers. Theoretically the effect of strain can be studied by simply band centers of the reacting metal atoms.
straining the slab. Examples of continuous changes in the d-
band center and in the stability of adsorbed CO due to strain 4. Variations due to alloying
are included in Fig. 4. We note that the effect due to vari-
ations in the number of layers of a thin film of metals on Effects due to alloying can also be understood in terms of
another can also be described in terms of the d-band model d-band shifts. This is already evident from Fig. 3. Fig. 5 shows
[28,29]. this in more detail. By considering a Pt(1 1 1) surface where a
Similar structural effects can be found for atomic chemisorp- series of different 3d metals have been sandwiched between the
tion, see the middle panel of Fig. 4. Again low coordinated first and second layer one can study the effect of second layer
atoms at steps bind adsorbates stronger and have lower barriers atoms on the reactivity of a Pt(1 1 1) overlayer. Such near-surface
for dissociation than surfaces with high coordination numbers alloys [35], or “skins” have been extensively studied as oxygen
and lower d-band centers. We note that the finding that the reduction catalysts in PEM fuel cells [36–38]. The d-states of
correlation with the d-band center is independent on the adsor- the surface Pt atoms are shifted down in energy as the second
bate and hence on the energy of the valence levels interacting layer metal is chosen further to the left in the periodic table.
with the metal surface illustrates the generality of the d-band The O and H adsorption energies show the same trends: as the
model. d-band center is shifted up in energy towards the Fermi level the
The d-band model thus explains the many observations that bond becomes stronger and stronger.
steps form stronger chemisorption bonds than flat surfaces For the near surface alloys the bandwidth changes by the
[25,26,30–34]. hybridization of the d-states of the surface Pt atoms with the
 T. Bligaard, J.K. Nørskov / Electrochimica Acta 52 (2007) 5512–5516 5515

Fig. 5. (a) Adsorption energy of H2 and O2 vs. d-band center on different sandwich structures. (b) The effect on the d-band of sandwiching a guest metal layer as
the first subsurface layer under a Pt surface. From Ref. [39].

second layer atoms. Such an indirect interaction can also be

Fig. 6. Electrochemically determined variations in the hydrogen adsorption
energy for different Pd overlayers as a function of the calculated d-band shifts.
From Ref. [44].
termed a ligand effect—the metal ligands of the surface atoms
are changed. Similar effects can be found for metal overlayers,
where a monolayer of one metal is deposited on top of another
metal. Here there is an additional effect relating to the fact that
the overlayer usually takes the lattice constant of the substrate.
For metal overlayers we therefore find a combination of ligand
and strain effects. Again the d-band centers are found to describe
changes in adsorption energies quite well [40–43]. This is illus-
trated in Fig. 6 showing electrochemically determined variations
in the hydrogen adsorption energy for different Pd overlayers as
a function of the calculated d-band shifts [44].
The fact that the reactivity of a given metal can be varied
substantially by depositing it on another metal provides an
elegant way of controlling the reactivity of a given metal.
Knowing how the d-band center for a given metal changes
when it is deposited on top of another provides a good starting
point for choosing interesting metal combinations. Again

Fig. 7. Changes in the d-band centers for monolayer overlayers on transition metal substrates. From Ref. [45].
5516 T. Bligaard, J.K. Nørskov / Electrochimica Acta 52 (2007) 5512–5516
DFT calculations can be used to systematically explore the
possibilities as shown in Fig. 7.
If, for instance, one wants a surface that bonds CO a little
weaker than Pt(1 1 1), then Fig. 6 suggests that putting Pt on top
of Fe, Co, Ni, Cu, Ru, Rh, and Ir should give the desired result
because the d-bands of Pt are shifted down relative to Pt(1 1 1) for
these substrates. This is important in looking for anode catalysts
for PEM fuel cells where poisoning by CO is a severe problem
and a surface that binds CO weaker (but still dissociates H2 )
is desirable. Such effects have been directly observed in single
crystal experiments [46,47] and in fuel cells [48–50].
A number of spectroscopic methods give information relat-
ing to d-band shifts [51]. Ross, Markovic and coworkers have
developed synchrotron-based high resolution photoemission
spectroscopy, to directly measure d-band centers giving results
in good agreement with the DFT calculations [52]. Another pos-
sibility is to exploit that fact that in some cases a shift in the
d-states can be measured as a core-level shift, as the d-states and
the core levels shift together [53,54]. This can explain the cor-
relations between surface core level shifts found by Rodriguez
and Goodman [55] for a number of metal overlayers and similar
results [56] for fuel cell catalysis by Watanabe and coworkers
[37].
Acknowledgments
The authors wish to acknowledge support from the Danish
Research Agency through grant 26-04-0047, from the Danish
Center for Scientific Computing through grant HDW-1103-06.
The Center for Atomic-scale Materials Design is sponsored by
the Lundbeck Foundation.
References
[1] W. Kohn, Rev. Mod. Phys. 71 (1999) 1253.
[2] J.K. Nørskov, M. Scheffler, H. Toulhoat, MRS Bull. 31 (2006) 669.
[3] P. Sabatier, Ber. Deutsch. Chem. Gesellshaft 44 (1911) 1984.
[4] T. Bligaard, J.K. Nørskov, S. Dahl, J. Matthiesen, C.H. Christensen, J.
Sehested, J. Catal. 224 (2004) 206.
[5] K. Honkala, A. Hellman, I.N. Remediakis, A. Logadottir, A. Carlsson, S.
Dahl, C.H. Christensen, J.K. Nørskov, Science 307 (2005) 555.
[6] A. Hellman, E.J. Baerends, M. Biczysko, T. Bligaard, C.H. Christensen,
D.C. Clary, S. Dahl, R. van Harrevelt, K. Honkala, H. Jonsson, G.J. Kroes,
M. Luppi, U. Manthe, J.K. Nørskov, R.A. Olsen, J. Rossmeisl, E. Skulason,
C.S. Tautermann, A.J.C. Varandas, J.K. Vincent, J. Phys. Chem. B 110
(2006) 17719.
[7] A. Logadottir, T.H. Rod, J.K. Nørskov, B. Hammer, S. Dahl, C.J.H. Jacob-
sen, J. Catal. 197 (2001) 229.
[8] A.B. Anderson, Y. Cai, J. Phys. Chem. B 108 (2004) 9829.
[9] Y. Cai, A.B. Anderson, J. Phys. Chem. B 108 (2004) 19917.
[10] J. Greeley, M. Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910.
[11] G.S. Karlberg, Phys. Rev. B 74 (2006) 153414.
[12] J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402.
[13] T.E. Shubina, M.T.M. Koper, Electrochem. Commun. 8 (2006) 703.
[14] P. Vassilev, R.A. van Santen, M.T.M. Koper, J. Chem. Phys. 122 (2005)
054701.
[15] A. Roudgar, A. Gross, Chem. Phys. Lett. 409 (2005) 157.
[16] Y. Okamoto, O. Sugino, Y. Mochizuki, T. Ikeshoji, Y. Morikawa, Chem.
Phys. Lett. 377 (2003) 236.
[17] M. Otani, O. Sugino, Phys. Rev. B 73 (2006) 115407.
[18] J.K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J.R. Kitchin, T.
Bligaard, H. Jonsson, J. Phys. Chem. B 108 (2004) 17886.
[19] J.K. Nørskov, T. Bligaard, A. Logadottir, J.R. Kitchin, J.G. Chen, S. Pan-
delov, U. Stimming, J. Electrochem. Soc. 152 (2005) J23.
[20] R. Parsons, Trans. Faraday Soc. 94 (1958) 1059.
[21] J. Greeley, T.F. Jaramillo, J. Bonde, I. Chorkendorff, J.K. Nørskov, Nature
Mater. 5 (2006) 909.
[22] B. Hammer, J.K. Nørskov, Adv. Catal. 45 (2000) 71.
[23] B. Hammer, J.K. Nørskov, in: R. Lambert, G. Pacchioni (Eds.), Theory
of adsorption and surface reactions in NATO ASI Series E 331, Kluwer
Academic Publishers, Dordrecht, 1997.
[24] B. Hammer, O.H. Nielsen, J.K. Nørskov, Catal. Lett. 46 (1997) 31.
[25] G.A. Somorjai, Introduction to Surface Chemistry and Catalysis, Wiley,
New York, 1994.
[26] J.T. Yates, J. Vac. Sci. Technol. A 13 (1995) 1359.
[27] M.A. van Hove, R.J. Koestner, P.C. Stair, J.P. Biberian, L.L. Kesmodel, I.
Bartos, G.A. Somorjai, Surf. Sci. 103 (1981) 189.
[28] B. Hammer, Top. Catal. 37 (2006) 3.
[29] A. Roudgar, A. Gross, J. Electronanal. Chem. 548 (2003) 121.
[30] G.A. Somorjai, B.E. Bent, Prog. Colloid Polym. Sci. 70 (1985) 38.
[31] C.R. Henry, C. Chapon, C. Goyhenex, R. Monot, Surf. Sci. 272 (1992) 283.
[32] R. van Hardeveld, A. van Montfoort, Surf. Sci. 4 (1966) 396.
[33] C.E. Tripa, T.S. Zubkov, J.T. Yates, M. Mavrikakis, J.K. Nørskov, J. Chem.
Phys. 111 (1999) 8651.
[34] G. Mills, M.S. Gordon, H. Metiu, J. Chem. Phys. 118 (2003) 4198.
[35] J. Greeley, M. Mavrikakis, Nature Mater. 3 (2004) 810.
[36] N.M. Markovic, P.N. Ross, Surf. Sci. Rep. 45 (2002) 121.
[37] T. Toda, H. Igarashi, H. Uchida, M. Watanabe, J. Electrochem. Soc. 146
(1999) 3750.
[38] J.L. Zhang, M.B. Vukmirovic, K. Sasaki, A.U. Nilekar, M. Mavrikakis,
R.R. Adzic, J. Am. Chem. Soc. 127 (2005) 12480.
[39] J.R. Kitchin, J.K. Nørskov, M.A. Barteau, J.C. Chen, J. Chem. Phys. 120
(2004) 10240.
[40] O.M. Løvvik, R.A. Olsen, J. Chem. Phys. 118 (2003) 3268.
[41] A. Roudgar, A. Gross, Phys. Rev. B 67 (2003) 33409.
[42] J.S. Filhol, D. Simon, P. Sautet, J. Am. Chem. Soc. 126 (2004) 3228.
[43] J. Meier, J. Schiøtz, P. Liu, J.K. Nørskov, U. Stimming, Chem. Phys. Lett.
390 (2004) 440.
[44] L.A. Kibler, A.M. El-Aziz, R. Hoyer, D.M. Kolb, Angew. Chem. Int. Ed.
44 (2005) 2080.
[45] A. Ruban, B. Hammer, P. Stoltze, H.L. Skriver, J.K. Nørskov, J. Mol. Catal.
A 115 (1997) 421.
[46] R.J. Behm, Acta Phys. Pol. 93 (1998) 259.
[47] J.C. Davies, B.E. Hayden, D.J. Pegg, Electrochim. Acta 44 (1998) 1181.
[48] G. Hoogers, D. Thompsett, CATTECH 3 (1999) 106.
[49] H. Igarashi, T. Fujino, Y. Zhu, H. Uchida, M. Watanabe, Phys. Chem. Chem.
Phys. 3 (2001) 306.
[50] P. Strasser, Q. Fan, M. Devenney, H.W. Weinberg, P. Liu, J.K. Nørskov,
Phys. Chem. B 107 (2003) 11013.
[51] D.P. Woodruff, T.A. Delchar, Modern Techniques of Surface Science, Cam-
bridge University Press, Cambridge, 1986.
[52] B.S. Mun, C. Lee, V. Stamenkovic, N.M. Markovic, P.N. Ross, Phys. Rev.
B 71 (2005) 115420.
[53] M. Weinert, R.E. Watson, Phys. Rev. B 51 (1995) 17168.
[54] D. Hennig, M.V. Ganduglia-Pirovano, M. Scheffler, Phys. Rev. B 53 (1996)
10344.
[55] J.A. Rodriguez, D.W. Goodman, Science 257 (1992) 897.
[56] B. Hammer, Y. Morikawa, J.K. Nørskov, Phys. Rev. Lett. 76 (1996) 2141.